Vat dyestuff and process of making same



ldatented Jan; 21', 193

TENT oFF nnnsr HONOLD, or ,Fncnnnnnm, NEAR assrenon TO e-nn ANILINEwonKs,

TIDN OF DELAWARE nnanKhon'r-onTnn-Mam, me, or new YORK, N. a, a cone VATDYESTUFF AND PROCESS OF MAKHTG SAME No Drawing. a ncatmn' filedSeptember 26, 1927, Serial No. seams, and in Germany llctolbel a, teen.7

l have found that by treating with an al-' kaline condensing agent abenzanthrone com: pound containing one or more arylsulfamino- (aryl-SO-NH-) groups inits molecule valuable vat dyestufl's are obtainablebelonging to the dibenzanthrone or isodibenzanthrone series orrepresenting mixtures of both types.

In ,conse uence of the solubility in alkalis of the aryl- O -NH-groupscontaining starting materials the condensation process runs particularlysmoothly. A Y

My invention is based on the surprising fact that in the course of thealkaline fusion the behaviour of the arylsulfamino-groups is differentaccording to their-positions in the benzanthrone molecule: Thearyl-sulfaminogroups standing in'2- or Bz-l-positions are split up inthe course of the reaction, whereas the arylsulfaininogroups standing inother than theafor'esaid positions remain unattacked byxthe reactingagentand are still present in the molecule of the reaction products.These latter arylsulfaminogroups can be transformed into aminogrou s bytreating the reaction products with acid saponifying agents,particularly with sulfuric acid."

The dyestuffs thus obtained contain free aminogroups intheir molecule,they differ essentially from the dyestulfs obtainable by. condensingwith alkaline acting agents the corresponding aminobenzanthronesthemselves (probably the aminogroup being attacked by the alkali appliedin such a condensation).

The benzanthrone compounds suitable for my process may contain besidesthe arylsulfv amlnogroups further substituents, they correall spond tothe general formula:

tions besides the -NH-SO -aryl-groups halogens, alkyl-, alkoxy-,hydrozry, and thioetherand amino-groups, v

As alkaline condensing agents there may be used a caustic alkali inaqueous or alcoholic solution or with the addition of aniline,sodiumaniline, s'odiumethylate or a similar acting agent. Y I

The vat dyestuifs thus obtained are when dry bluish to greyto blackpowders, soluble in concentrated sulfuric acid with a greenish to olivetoblack color, they dye cotton from .in which formula X means hydrogenor a i v e0 as nonreactlve substituents in the Y-poslq a bluish toviolet vat bluish to grey to black shades'of an excellent fastness.

The new one or more .NH-SO -arylgroups containing derivatives of benzenethrone used as starting materials for my process may be obtained eitherby treating the corresponding aminoderivatives with an arylsulfochlorideor by condensing the correspending halogenated derivatives with anarylsulfamide, advantageously with addition of an agent neutralizing theacid set free and of a catalyst in presence of a suitable diluent Inorder to further illustrate my invention the following examples aregiven, the parts being by weight and all temperatures in centigradedegrees, but it is understood, that my invention is not limited to theparticular products or reacting conditions mentioned therein. a

Example 1 At about 160 (temperature of the bath.) 10 parts ofBz-l-paratoluenesulfaminobenzanthrone are introduced into a moltenrniature of 50 parts of caustic potash and 5 parts of alcohol, a

' lllie benz'anthrene compound s lmlnfidll ately dissolved and themolten mass turns to a dark red coloration. After having increased thetemperature of the bath for about an hour to about 210, the mass isdiluted with water and the leuco-compound of the dyestufi formedoxidized by introducing a current of air or by means of other oxidizingagents. The dyestuff isolated in the usual manner is soluble inconcentrated sulfuric acid with a green color, it dyes cotton from abluish violet vat reddish blue shades.

It corresponds probably to the following formula:

The -Bz 1 5 paratoluenesulfaminobenzanthrone used for the process of theformula:

NH-SOv-OOH Example 2 At about 170 (temperature of the bath) 20 parts of.6-Bz-1-diparatoluenesulfaminobenzanthrone are introduced into a moltenmixture of 100 parts of caustic alkali and 10 parts of alcohol and thetemperature ofv the bluish violet colored mass is increased to about 220during one hour. When the formation of dyestufl' is finished the mass ispoured on water and the leucc--compound conmanner. The new condensationproduct thus obtained separates partly as potassium lated.

Itcorresponds probably to the formula:

2 It dissolves in concentrated sulfuric acid with an olive black color,it forms with hydrosulfite and alkalis a bluish violet vat dyeing cottontherefrom grey to black shades of an excellent fastness.

Instead of caustic alkalis in presence of alcohol other alkalinecondensing agents may be used for the process, such as for instancecaustic alkalis with addition of aniline, s0- diumaniline andsodiumethylate. A dyestuff of analogous properties is obtained bytreating with alkaline condensing agents theG-paratoluenesulfaminobenzanthrone, the Bz-l-position of which issubstituted by an S-containing group such as -SCH S-, S0 H The 6 Bz 1 diparatoluenesulfaminobenzanlthrone used for the process of the formu a:

may be prepared in the aforesaid manner for x 05 tained in the solutionis oxidized in the usual instance either by heating G-Bz-l-diaminoble indilute caustic soda solution with a violet color and in concentratedsulfuric acid with 1 .a dark red color.

tilt

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When replacing it by the equivalent amount of dpara-toluenesulfaminb Bz-1 chlorobenzanthrone and working otherwise as described above adyestufi of the same lrind is obtained, by usingBz-Q-benzenesulfaminobenzanthrone and saponitying thebenzenesullaminogroups contained in the molecule of the condensationproduct to aminogroups a dyestufl is formed,

insoluble in caustic alkali solutions, soluble in concentrated sulfuricacid with a violet black color; it forms with an alkaline hydrosulfitesolution a bluish vat, from which cotton is dyed greenish grey shades ofan excellent fastness.

ll claim:

1. The process which comprises treating with an alkaline condensingagent a benzanthrone compound of the general formula:

in which formula K meanshydrogen or a substituent of the group includingarylsultamino, halogen, mercaptane, sul de, thioether, and sulfinic acidand the Ys represent hydrogen atoms, of which oneor more may be replacedby a monovalent substituent, at

least one X or Y standing for a group --NH-SO -aryl.

2. The process which comprises treating with an alkaline condensingagent a benzen throne compound of the general formula:

v in which formula X means hydrogen or a substituentof the groupincluding arylsult amino, halogen, mercaptane, ether, and sulfinic acidand the We represent hydrogen atoms, of which one or more may bereplaced by a monovalent substituent, at least one Y standing for agroup -NH-SU -aryl.

3. The process which comprises treating with an alkaline condensingagent a benzanthrone compound of the general formula:

sulfide, thioin which formula Xmeanshydrogen or a substituent of thegroup including arylsulfamino, halogen, mercaptane, sulfide, thio ether,and sulfinic acid and the Ys represent hydrogen atoms, of which one ormore may be replaced by a monovalent snbstituent, at least one Ystanding for a cup -MI-SO -aryl, and treating the pr nets ofcondensation thus obtained with acid saponitying agents for saponifyingthe ary sulfaminogroups still contained to aminogroups.

4. As new compounds the rat dyestutts, being when dry grey to blackpowders, soluble in concentrated sulfuric acidwith a greenish to oliveto black color, forming with an alkaline hydrosulfite solution a bluishrat and dyeing cotton therefrom grey to his ck shades of an excellenttastness and being substantially identical with products, obtainable bytreating with alkaline condensing agents a benzanthrone compound of thegeneral formula:

in which formula .Xmeans hydrogen or a substituent of the groupincluding arylsul amino, halogen, mercaptane, sulfide, thioether, andsulfinic acid and the Ys represent hydrogen atoms ml which one or moremay be replaced by a inonovalent anhstituent, at least one standing fora. group NltLSQ -aryl, and by treating the products saponifyinarylsulfaminogroups still contained to aminoof condensation thusobtained with acid agents for saponifying' the groups.

5. As a new compound the vat dyestufi,

being when dry a blackish powder, soluble 'in concentrated sulfuric acidwith an olive black color, forming with an alkaline hydrosulfitesolutlon a bluish violet vat and dyeing cotton therefrom grey-blackshades of an excellent fastness, and being substantially identical witha product obtainable by treating with an alkaline condensing agent abenzanthrone compound of the formula:

N 11-8 0:- aryl in which formula X means hydrogen or a substituent ofthe group including arylsulfamino, halogen, mercaptane, sulfide,thioether, and sulfinic acid, and treating the product of condensationthus obtained with acid saponifying agents for saponifying the'arylsulfaminogroups to aminogroups.

6. The process which comprises introducing about 10 parts of a compoundof the general formula:

NRSOOCHJ wherein X represents hydrogen or the paratoluenesulfaminogroup, into a molten mixture of about 50 arts of caustic alkali andabout 5 parts 0 alcohol, heating the reaction mixture to a temperatureof from about 210 to about 220 C. for about one hour, and isolating thedyestufi in the usual 0 manner.

In testimony whereof I aflix m signature.

ERNST ONOLD.

